US8835628B2ActiveUtilityPatentIndex 43
Stable and highly tunable metathesis catalysts
Est. expiryJul 30, 2030(~4.1 yrs left)· nominal 20-yr term from priority
C07C 67/333B01J 2231/54C07D 207/20B01J 31/2208B01J 2531/821B01J 31/2278B01J 31/12B01J 31/2273C07F 15/0046
43
PatentIndex Score
1
Cited by
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References
40
Claims
Abstract
The present invention relates to catalytically active compounds of the general formula (1) that are highly tunable, as well as to a method of their preparation and their use in any type metathesis reaction. The new compounds of the present invention comprise activation sites that allow for specific catalyst design. Particularly, side chains and ligands allow efficient activity and specificity control of the catalysts of the present invention.
Claims
exact text as granted — not AI-modifiedThe invention claimed is:
1. A compound of formula 1,
wherein,
X and X′ are anionic ligands;
L is an uncharged ligand;
z is a methylene or a carbonyl group;
each of a, b and c is independently H, NO 2 or a substituted or unsubstituted, charged or uncharged hydrocarbon group comprising up to 20 carbon atoms or a heteroatom-containing hydrocarbon group comprising up to 20 carbon atoms and one or more heteroatoms;
each of R1, R2 and R3 is independently H or a substituted or unsubstituted, charged or uncharged hydrocarbon group comprising up to 20 carbon atoms or a heteroatom-containing hydrocarbon group comprising up to 20 carbon atoms and optionally comprising one or more heteroatoms.
2. The compound of claim 1 , wherein each of X and X′ is a halogen.
3. The compound of claim 1 , wherein each of a, b and c is independently selected from the group consisting of H; —NO 2 ; C 1-12 -alkyls; C 5-12 -cycloalkyls; C 1-12 -alkoxys; cyano; aryls; heteroaryls, phenyl radicals optionally substituted by a radical selected from the group consisting of C 1-6 -alkyls and C 1-6 -alkoxys; monohalogenated and polyhalogenated aryl radicals and hetero-aryl radicals; monohalogenated and polyhalogenated C 1-6 -alkyl radicals; monohalogenated and polyhalogenated C l-6 -alkyl-substituted aryl radicals; C 1-6 -alkylcarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkylcarbonyl radicals; C 1-6 -alkoxycarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkoxycarbonyl radicals; arylcarbonyl radicals; monohalogenated and polyhalogenated arylcarbonyl radicals; aryloxycarbonyl radicals; monohalogenated and polyhalogenated aryloxycarbonyl radicals; —(C═O)—N(R a ) 2 radicals wherein R a is a C 1-6 -alkyl or aryl radical; —NH—(C═O)—R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; C 1-6 -alkylsulfonyl radicals; C 1-6 -alkylsulfinyl radicals; —P(═O)(R a ) 2 radicals wherein R a is a C 1-6 alkyl or aryl radical; —NH—SO 2 —R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; (SO 2 )NR a 2 radicals wherein R a is a C 1-6 -alkyl or a aryl radical; and P(═O)(OR a )(R a ) radicals wherein R a is a C 1-6 -alkyl or aryl radical.
4. The compound of claim 1 wherein a, b and c are each H.
5. The compound of claim 1 wherein R1 is H, a C 2-12 -alkenyl, a C 2-12 -alkynyl or an aryl.
6. The compound of claim 1 wherein R1 is H.
7. The compound of claim 1 wherein R2 is H, a C 1-12 -alkyl, a C 5-12 -cycloalkyl, a C 7-18 -aralkyl or an aryl.
8. The compound of claim 1 wherein R2 is a methyl-, ethyl- or isopropyl-group.
9. The compound of claim 1 , wherein R3 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-18 -aralkyls, aryls, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro-alkyls, nitriles, and radicals selected from the group consisting of ketones COR4, esters CO 2 R4, oxalates COCO 2 R4, sulfones SO 2 R4 and amides CONHR4 wherein, R4 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-18 -aralkyls, aryls, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro-alkyls, and nitriles.
10. The compound of claim 1 , wherein,
z is methylene, and
R3 is of the formula R3 a or R3 b :
wherein A − is selected from the group consisting of F − , Cl − , Br − , I − , tetrafluoroborate BF 4 − , hexafluorophosphate PF 6 − and bis(trifluoromethylsulfonyl)amide NTf 2 − .
11. The compound of claim 1 ,
wherein,
R3 is of the formula R3 c , R3 d , R3 e , R3 f , R3 g , R3 h , R3 i , R3 j , R3 k , R3 l , R3 m , R3 n , R3 o or R3 p :
12. The compound of claim 1 ,
wherein L is a phosphine P(R8) 3 or a phosphate P(OR9) 3 wherein R8 and R9 are each independently a C 1-6 -alkyl, a C 5-12 -cycloalkyl or an aryl.
13. The compound of claim 1 ,
wherein L is a ligand of the formula L1, L2, L3 or L4:
wherein R10 and R11 are each independently a substituted or an unsubstituted hydrocarbon comprising 1 to 30 carbon atoms, and
R12 and R13 are each independently H, a C 1-6 -alkyl optionally substituted by a alkoxy radical OR15, or aryl optionally substituted by a alkoxy radical OR15, or form a 3- or 4-membered alkylene bridge, wherein R15 is selected from the group consisting of C 1-20 -alkyls, aryls and C 7-18 -aralkyls, and
g and g′ are each a halogen.
14. The compound of claim 13 , wherein R10 and R11 are each independently a C 1-30 -alkyl optionally substituted by an alkoxy radical OR15, a C 2-30 -alkenyl optionally substituted by an alkoxy radical OR15, aryl optionally substituted by an alkoxy radical OR15, an aminoalkyl or an aminocycloalkyl.
15. The compound claim 1 , wherein L is a ligand of the formula L1 a , L1 b , L1 c , L1 d , L1 e , L1 f or L1 g :
16. A method comprising contacting one or more chemical reactants with a catalyst comprising the compound of claim 1 to promote a chemical reaction of the reactants.
17. The method of claim 16 wherein said chemical reaction is a metathesis reaction.
18. A method of preparing the compound of claim 1 comprising reacting a compound of formula (2)
with a ruthenium complex of formula (3)
wherein,
LG is a leaving group
R14 is H or a C 1-12 -alkyl,
each of R16 and R17 is independently H, a C 1-6 -alkyl, optionally substituted by one or more halogens, or an aryl, optionally substituted by one or more halogens or by a C 1-6 -alkyl; or R16 and R17 together form a 5- to 12-membered aliphatic and/or aromatic ring system, optionally substituted by one or more halogens, a C 1-6 -alkyl or by an aryl.
19. The method of claim 18 , wherein each of X and X′ is a halogen.
20. The method of claim 18 , wherein each of a, b and c is independently selected from the group consisting of H; —NO 2 ; C 1-12 -alkyls; C 5-12 -cycloalkyls; C 1-12 -alkoxys; cyano; aryls; heteroaryls; phenyl optionally substituted by a radical selected from the group consisting of C 1-6 -alkyls and C 1-6 -alkoxys; monohalogenated and polyhalogenated aryl radicals and hetero-aryl radicals; monohalogenated and polyhalogenated C 1-6 -alkyl radicals; monohalogenated and polyhalogenated C 1-6 -alkyl-substituted aryl radicals; C 1-6 -alkylcarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkylcarbonyl radicals; C 1-6 -alkoxycarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkoxycarbonyl radicals; arylcarbonyl radicals; monohalogenated and polyhalogenated arylcarbonyl radicals; aryloxycarbonyl radicals; monohalogenated and polyhalogenated aryloxycarbonyl radicals; —(C═O)—N(R a ) 2 radicals wherein R a is a C 1-6 -alkyl or aryl radical; —NH—(C═O)—R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; C 1-6 -alkylsulfonyl radicals; C 1-6 -alkylsulfinyl radicals; —P(═O)(R a ) 2 radicals wherein R a is a C 1-6 -alkyl or aryl radical; —NH—SO 2 —R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; (SO 2 )NR 2 a radicals wherein R a is a C 1-6 -alkyl or aryl radical; and P(═O)(OR a )(R a ) radicals wherein R a is a C 1-6 -alkyl or aryl radical.
21. The method of claim 18 , wherein a, b and c are each H.
22. The method of claim 18 , wherein R1 is H, a C 2-12 -alkenyl, a C 2-12 -alkynyl or an aryl.
23. The method of claim 18 , wherein R1 is H.
24. The method of claim 18 , wherein R2 is H, a C 1-12 -alkyl, a C 5-12 cycloalkyl, a C 7-18 -aralkyl or an aryl.
25. The method of claim 18 , wherein R2 is a methyl-, ethyl- or isopropyl-group.
26. The method of claim 18 , wherein R3 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-8 -aralkyls, aryls, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro alkyls, nitriles, and radicals selected from the group consisting of ketones COR4, esters CO 2 R4, oxalates COCO 2 R4, sulfones SO 2 R4 and amides CONHR4 wherein, R4 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-18 -aralkyls, aryl, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro-alkyls, and nitriles.
27. The method of claim 18 , wherein,
z is methylene, and
R3 is of the formula R3 a or R3 b :
wherein A − is selected from the group consisting of F − , Cl − Br − , I − , tetrafluoroborate BF 4 − , hexafluorophosphate PF 6 − and bis(trifluoromethylsulfonyl)amide NTf 2 − .
28. The method of claim 18 , wherein, R3 is of the formula R3 c , R3 d , R3 e , R3 f , R3 g , R3 h , R3 i , R3 j , R3 k , R3 l , R3 m , R3 n , R3 o or R3 p :
29. The method of claim 18 , wherein L is a phosphine P(R8) 3 or a phosphate P(OR9) 3 and R8 and R9 are each independently a C 1-6 -alkyl, a C 5-12 -cycloalkyl or an aryl.
30. The method of claim 18 , wherein L is a ligand of the formula L1, L2, L3 or L4:
wherein R10 and R11 are each independently a substituted or an unsubstituted hydrocarbon comprising 1 to 30 carbon atoms, and
wherein R12 and R13 are each independently H, a C 1-6 -alkyl optionally substituted by a alkoxy radical OR15, or aryl optionally substituted by a alkoxy radical OR15, or form a 3- or 4-membered alkylene bridge, wherein R15 is selected from the group consisting of C 1-20 -alkyls, aryl and C 7-18 -aralkyls, and
g and g′ are each a halogen.
31. The method of claim 30 , wherein R10 and R11 are each independently a C 1-30 -alkyl optionally substituted by a alkoxy radical OR15, a C 2-30 -alkenyl optionally substituted by a alkoxy radical OR15, an aryl optionally substituted by a alkoxy radical OR15, an aminoalkyl or an aminocycloalkyl.
32. The method of claim 18 , wherein L is a ligand of the formula L1 a , L1 b , L1 c , L1 d , L1 e , L1 f or L1 g :
33. The compound of claim 1 wherein each of X and X 1 is independently Cl or Br.
34. The compound of claim 13 wherein each of g and g 1 is independently Cl or Br.
35. The method of claim 17 wherein the metathesis reaction is a ring-closing metathesis (RCM) reaction, a cross-metathesis (CM) reaction, or a ring-opening metathesis polymerization (ROMP) reaction.
36. The method of claim 18 wherein
LG is a phosphine P(R8) 3 where R8 is selected from the group consisting of C 1-6 -alkyls; C 5-12 -cycloalkyls; and aryls;
R14 is H or a C 1-12 -alkyl; and
R16 and R17 are each independently H, a C 1-6 -alkyl optionally substituted with one or more halogens, an aryl, optionally substituted with one or more halogens or a C 1-6 -alkyl; or R16 and R17 together form a 5- to 12-membered aliphatic or aromatic ring system, optionally substituted with one or more halogens, a C 1-6 -alkyl or an aryl.
37. The method of claim 18 wherein
LG is a pyridine or a pyridine substituted with a charged or uncharged hydrocarbon group comprising up to 20 carbon atoms,
R14 is a methyl group; and
R16 and R17 together form an indenylidene system.
38. The method of claim 19 wherein each of X and X 1 is independently Cl or Br.
39. The method of claim 30 wherein each of g and g 1 is independently Cl or Br.
40. A compound of formula 1,
wherein,
each of X and X′ is a an anionic ligand independently selected from the group consisting of halogens;
z is a methylene or a carbonyl group;
each of a, b and c is independently selected from the group consisting of H; —NO 2 ; C 1-12 -alkyls; C 5-12 -cycloalkyls; C 1-12 -alkoxys; cyano; aryls; heteroaryls, phenyl radicals optionally substituted by a radical selected from the group consisting of C 1-6 -alkyls and C 1-6 -alkoxys; monohalogenated and polyhalogenated aryl radicals and hetero-aryl radicals; monohalogenated and polyhalogenated C 1-6 -alkyl radicals; monohalogenated and polyhalogenated C 1-6 -alkyl-substituted aryl radicals; C 1-6 -alkylcarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkylcarbonyl radicals; C 1-6 -alkoxycarbonyl radicals; monohalogenated and polyhalogenated C 1-6 -alkoxycarbonyl radicals; arylcarbonyl radicals; monohalogenated and polyhalogenated arylcarbonyl radicals; aryloxycarbonyl radicals; monohalogenated and polyhalogenated aryloxycarbonyl radicals; —(C═O)—N(R a ) 2 radicals wherein R a is a C 1-6 -alkyl or aryl radical; —NH—(C═O)—R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; C 1-6 -alkylsulfonyl radicals; C 1-6 -alkylsulfinyl radicals; —P(═O)(R a ) 2 radicals wherein R a is a C 1-6 -alkyl or aryl radical; —NH—SO 2 —R a radicals wherein R a is a C 1-6 -alkyl or aryl radical; (SO 2 )NR 2 a radicals wherein R a is a C 1-6 -alkyl or aryl radical; and P(═O)(OR a )(R a ) radicals wherein R a is a C 1-6 -alkyl or aryl radical;
R1 is selected from the group consisting of H, C 2-12 -alkenyls, C 2-12 -alkynyls, and aryls;
R2 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-18 -aralkyls, and aryls; and
R3 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-18 -aralkyls, aryls, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro-alkyls, nitriles, ketone radicals of the form COR4, ester radicals of the form CO 2 R4, oxalate radicals of the form COCO 2 R4, sulfone radicals of the form SO 2 R4 and amide radicals of the form CONHR4 where R4 is selected from the group consisting of H, C 1-12 -alkyls, C 5-12 -cycloalkyls, C 7-8 -aralkyls, aryls, C 1-12 -halogeno-alkyls, C 1-12 -ammonium-alkyls, C 1-12 -pyridinum-alkyls, C 1-12 -aldehyde-alkyls, C 1-12 -nitro-alkyls, and nitriles; and
L is an uncharged ligand selected from the group consisting of phosphines P(R8) 3 and phosphates P(OR9) 3 where each R8 and R9 is independently selected from the group consisting of C 1-6 -alkyls, C 5-12 -cycloalkyls and C 5-12 -aryls, and ligands of the formula L1, L2, L3 or L4:
wherein R10 and R11 are each independently a C 1-30 -alkyl optionally substituted by an alkoxy radical OR15, a C 2-30 -alkenyl optionally substituted by an alkoxy radical OR15, aryl optionally substituted by an alkoxy radical OR15, an aminoalkyl or an aminocycloalkyl,
R12 and R13 are each independently H, a C 1-6 -alkyl optionally substituted by a alkoxy radical OR15, or aryl optionally substituted by a alkoxy radical OR15, or form a 3- or 4-membered alkylene bridge,
R15 is selected from the group consisting of C 1-20 -alkyls, aryls, and C 7-18 -aralkyls, and
g and g′ are each a halogen.Cited by (0)
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